Perspective

http://pubs.acs.org/journal/aelccp

Challenges in Lithium Metal Anodes for Solid-

State Batteries
Kelsey B. Hatzell,* Xi Chelsea Chen, Corie L. Cobb, Neil P. Dasgupta, Marm B. Dixit,
Lauren E. Marbella, Matthew T. McDowell, Partha P. Mukherjee, Ankit Verma,
Venkatasubramanian Viswanathan, Andrew S. Westover, and Wolfgang G. Zeier

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ABSTRACT: In this Perspective, we highlight recent progress

and challenges related to the integration of lithium metal
anodes in solid-state batteries. While prior reports have
suggested that solid electrolytes may be impermeable to lithium
metal, this hypothesis has been disproven under a variety of
electrolyte compositions and cycling conditions. Herein, we
describe the mechanistic origins and importance of lithium
filament growth and interphase formation in inorganic and
organic solid electrolytes. Multimodal techniques that combine
real and reciprocal space imaging and modeling will be necessary to fully understand nonequilibrium dynamics at these buried
interfaces. Currently, most studies on lithium electrode kinetics at solid electrolyte interfaces are completed in symmetric Li−
Li configurations. To fully understand the challenges and opportunities afforded by Li-metal anodes, full-cell experiments are
necessary. Finally, the impacts of operating conditions on solid-state batteries are largely unknown with respect to pressure,
geometry, and break-in protocols. Given the rapid growth of this community and the diverse portfolio of solid electrolytes, we
highlight the need for detailed reporting of experimental conditions and standardization of protocols across the community.

T here is considerable interest in replacing graphite

anodes in rechargeable batteries with Li metal because
of its high theoretical capacity (3860 mAh/g) and
large negative potential (−3.06 vs NHE).1 However, Li metal
is prone to unstable side reactions, leading to solid electrolyte
interphase (SEI) and dendrite formation when in contact with
most liquid electrolytes. These side effects can lead to
considerable safety concerns and a loss of efficiency. Solid
electrolytes that are chemically stable against Li metal may be
able to suppress these negative effects. However, there remain
several unknown aspects to the nature of ion transport and
kinetics at Li-metal|solid-electrolytes (Li-metal|SE) interfaces.
For future adoption, it is critical to understand Li-metal|SE
interfaces to mitigate Li filament formation, achieve reliable
power densities, and maintain a high Coulombic efficiency
over the cycling lifetime.
Controlling the morphology of Li metal during electro-
chemical stripping and plating processes at Li-metal|SE
interfaces is necessary for the realization of energy-dense Li-
metal solid-state batteries (SSBs).2−4 Li-metal SSBs could
potentially increase energy density and reduce space and
weight requirements (Figure 1a).5 However, achieving >10
mAh cm−2 cumulative capacity plated at failure, >3 mA cm−2
plating current density, >3 mAh cm−2 per cycle areal capacity,
and >80% fraction of Li passed per cycle are all necessary at
the device level to displace the current state-of-the-art graphite
anodes.4 Few reports come close to these targets because Li
metal is prone to interfacial instabilities and significant volume
changes. This Perspective summarizes the recent progress in
understanding Li-metal|SE interfaces for SSBs, with the goal of
ultimately controlling factors such as Li filament growth and
interfacial reaction/delamination during electrochemical cy-
cling. The mechanistic origins of lithium filament growth in
SEs is discussed with respect to interphase formation and
lithium mechanics. Next, the Perspective highlights state-of-
the-art characterization tools equipped to observe Li|SE
interfaces and discusses future needs, including techniques
that provide complementary chemical and structural informa-
tion. Finally, the Perspective concludes with a discussion of
Received: December 8, 2019
Accepted: February 18, 2020
Published: February 18, 2020

© 2020 American Chemical Society https://dx.doi.org/10.1021/acsenergylett.9b02668

922 ACS Energy Lett. 2020, 5, 922−934
ACS Energy Letters http://pubs.acs.org/journal/aelccp
Figure 1. Li-metal solid-state battery architecture. To achieve adequate rate performance, pressure (σ) is applied to the cell (a). The
morphology of the interface governs local ionic flux, pore formation in the Li-metal upon stripping, and Li filament growth (b). Li filament
growth in a polymer solid electrolyte is governed by electrolyte mechanics, transference number, and the presence of interfacial impurities
(c). Li filaments in inorganic SEs are attributed to electronic conductivity, microstructural properties, and interfacial contact (d).
frontiers in modeling and remaining open questions in the
quest for Li-metal SSBs (Figure 1a).
Lithium Penetration through Solid Electrolytes. Graphite has
been the standard anode material for decades because reactive
Li metal can lead to dendrite formation, short-circuits, and
fires. Concentration gradients across a cell can create excess
charge at an interface (local space charge) and induce
instabilities (e.g., dendrites). The term “Li dendrite” broadly
describes the formation of a wide range of nonplanar/branched
metal morphologies and may not accurately describe the
complex mechanisms involved in SEs (Figure 1b). Instead, we
suggest the use of the term Li filaments, and use this
terminology here. Li filaments through SEs plague SSBs,
leading to a loss of efficiency and cell failure. Understanding
the nature of this growth is imperative for next-generation
SSBs.
The term “Li dendrite” broadly de-
scribes the formation of a wide range
of nonplanar/branched metal mor-
phologies and may not accurately
describe the complex mechanisms
involved in SEs. Li filaments through
SEs plague SSBs, leading to a loss of
efficiency and cell failure. Understand-
ing the nature of this growth is
imperative for next-generation SSBs.
The current density at which a Li filament propagates across
a SE is known as the critical current density (CCD). The
magnitude of the CCD is important because it dictates the
power density of a cell. Low CCDs are generally ascribed to iR
losses that emerge as a result of interfacial impedances between
the SE and the electrodes. These interfacial impedances are
largely governed by chemical, electrochemical, and mechanical
stability issues at interfaces. Deconvoluting these loss
mechanisms and interpretation of CCD measurements can
be challenging because SEs may be susceptible to “soft shorts”
that can go undetected in symmetric cell experiments that
utilize thick lithium metal (>30 μm).4 Furthermore, the CCD
is dependent on cell stack pressure and plating capacity, and
thus, it is necessary to report detailed experimental conditions
(e.g., Li-metal thickness and stack pressure) to accurately
923
Perspective
interpret data.3 Recently, Sakamoto and co-workers described
a new terminology, critical stack pressure, which highlights the
pressure dependency in CCD measurements.3 This parameter
is an important additional metric for evaluating Li electrode
properties at SE interfaces. Pores in Li metal formed during
electrochemical dissolution (stripping) and uneven Li+ trans-
port at anode−electrolyte interfaces may be origins for
dendrite nucleation.6−8 A nominal stack pressure can aid in
mitigating pore formation during Li stripping. However, Li
filament growth and propagation occur upon Li plating. When
these occur simultaneously in Li−Li cells, the pressure will
significantly affect the CCD. However, is unclear exactly how
these effects will translate to full cells, where plating and
stripping are independent processes. Further work is necessary
to resolve differences between whole cell and symmetric
experiments.
Li filament growth at a solid polymer electrolyte (SPE)
interface is dependent on the electrolyte’s transference
number, the electrolyte’s mechanical properties, and Li-metal
impurities (Figure 1c). Ionic transport in SPEs (for example,
poly(ethylene oxide) (PEO)) mimics the transport character-
istics of liquid electrolytes and can be accurately described by
the concentrated solution theory for binary electrolytes based
on the Onsager−Stefan−Maxwell formalism.9 Thus, current
flux is a consequence of ion transport under both
concentration and potential gradients in the polymer electro-
lyte, with a transference number of the cation being less than
unity.8 Consequently, the CCD in SPEs is primarily
determined by the limiting current density, wherein the
cationic concentration goes to zero at Sand’s time, engendering
unmitigated dendritic growth.10 Sand’s time is inversely
proportional to the square of the anionic transference number,
and thus, single-ion solid conducting SEs (inorganic or
polymer) are theoretically stable against Li filament
growth.11,12 However, a large number of single-ion conducting
polymers have been developed without significant improve-
ments to the CCD.12,13
Monroe and Newman predicted that if the shear modulus of
a SPE exceeded 6 GPa, Li filaments could not penetrate the
SPE.6 Recent work by the Balsara group has shown that
improving the modulus can increase the CCD, especially at
high temperatures, but it cannot entirely eliminate Li filament
formation.14−17 Thus, neither the mechanical properties nor
the transference number of the SE can fully determine the
growth of Li filaments through SPEs. In models such as the
Monroe and Newman model, Li is assumed to be pure, which
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ACS Energy Lett. 2020, 5, 922−934
ACS Energy Letters http://pubs.acs.org/journal/aelccp
may not be fully representative of the interfacial composition.
X-ray imaging has shown that Li-metal surface impurities
(Li2O, Li3N, or Li2CO3) can cause inhomogeneities in the
local current density and promote the nucleation of Li
protrusions (Figure 1c).18−20 Thus, while increasing the elastic
modulus and transference number of SPEs is critical, the purity
of the Li-metal source and surface may play a significant role in
Li penetration at high current densities. Pretreatment strategies
may be necessary for integration of Li metal.21
Single-ion conducting inorganic SE (glass and/or ceramic)
have failure mechanisms that are distinctly different than that
of SPEs (Figure 1d). Metal filament formation has been
attributed to physical and/or microstructural properties of the
SE, Li-metal|SE interfacial contact, and/or electronic proper-
ties of the electrolyte (Figure 1d).22 Pioneering work on solid-
state Na β-alumina batteries revealed two modes for Na
filament formation. Mode 1 describes filament formation and
propagation with respect to SE microstructural features (grain
boundaries, voids, scratches, etc.). This failure mode is based
on Griffith’s theories of fracture mechanics and was used to
derive an empirical relationship for the critical current density
ÄÅ ÉÑ
of a Na β-alumina system22
ÅÅÅ π (1 − v 2)Fγeff 2 ÑÑÑij c 2 yz
icrit = ÅÅÅ ÑÑjj zz
ÅÅ ÑÑj 3 z
ÑÑÖk l {
ÅÇ 8VmEη
where v is Poisson’s ratio, F Faraday’s constant, γeff the surface
energy, Vm the molar volume of Na, E Young’s modulus, η the
Na viscosity, 2c the crack width, and l the crack length. In
simpler terms, the CCD is determined by the aspect ratio of
surface defects (c2/l3) such as voids, scratches, or cracks, the
wetting of the alkali metal to the solid electrolytes (γeff), and
the mechanical properties of the electrolyte. Temperature also
plays a key role as this will directly affect the surface wetting
(γeff) and viscosity of the alkali metal (η). Previously, it was
shown that heating and constant pressure enable improved
contact, lower interfacial resistances, and higher critical current
densities.23 In contrast, mode 2 describes how the electronic
properties of the SE governs filament growth.24,25 During
operation, Na β-alumina changes colors as the electronic
conductivity of the material changes. When the SE is
electrically conductive, Na can deposit within the SE and act
as a nucleation site for filament growth. These two growth
modes provide valuable insights into the driving mechanism
for filament propagation in Li SEs. Recent research with Li
metal strongly suggests that Li filament propagation is
analogous to that of the Na metal filament propagation.
Parallels between Na and Li filament growth mechanisms
can be drawn from a series of reports by Porz and Swamy.26,27
Porz et al.26 studied Li filament formation and growth in a
wide range of inorganic solid electrolytes (Li7La4Zr2O12,
crystalline β-Li3PS4, and lithium thiophosphate glasses).
Their work demonstrates that lithium filaments prefer to
grow through cracks and defects and that plating-induced
lithium infiltration can take place in pre-existing micro-
structural flaws. Later work by Swamy et al. observed that
lithium filaments preferentially grew at the electrode edge in
grain-boundary free, single-crystal LLZO. Preferential Li
growth at the electrode edge, rather than at engineered
defects, reveals that filament formation can be driven by local
electric-field hot spots. This current focusing leads to
preferential Li deposition and results in enhanced mechanical
stresses at these locations. Another recent paper by Westover
924
Perspective
et al.28 corroborates the role that current focusing and surface
flaws (e.g., grain boundaries) play on filament propagation. Li
filaments demonstrated preferential growth at artificial Lipon−
Lipon interfaces and completely avoided the bulk electrolyte.
Li filament penetration along the interface is attributed to
current focusing, the presence of Li2CO3 defects, and the
interfacial mechanical properties. All of these factors can
contribute to the relatively wide spread in reported CCD
values for Li-metal SSBs. There is currently a crucial need for
unified, standard operating protocols (ramp rate, current hold
duration, etc.) and standard cell architectures for CCD
measurements for effective comparison across the community.
Although the most well-studied mechanism for Li filament
penetration is mode 1 (microstructure, defect, etc.), a recent
paper by Han et al.29 highlighted mode 2 (electronic
conductivity) mechanisms. In situ neutron depth profiling
experiments revealed increases in Li-metal content within the
SE (Lipon, LLZO, and β-Li3PS4) during electrochemical
cycling. Increases in Li content within the SE suggests that
local depositions of Li metal can occur within the bulk SE
(Figure 1d). These deposits can act as nucleation sites for
filament growth and can cause a short circuit. Electron
microscopy30 and X-ray tomography31 results also showed
isolated Li deposits that support this finding. It has been
hypothesized that the SE electronic conductivity is responsible
for these localized Li deposits;32 however, recent theoretical
studies suggest that local reduction of La or Zr at the grain
boundaries33 or electrons trapped at surface defects may drive
deposition events.34 Further research is needed to fully
understand this mechanism, or combination of mechanisms,
and to guide the development of materials and engineering
solutions that enable high CCDs at room temperature.
Aside from SE properties, the mechanical properties of the
lithium metal anode also play an important role in Li filament
formation in SEs. Recent studies of the bulk mechanical
response of Li metal have demonstrated that power-law creep
is the dominant deformation mechanism over a wide range of
strain rates and temperatures.35,36 These results help contextu-
alize the evolution of mechanical stresses as Li is plated out at a
solid-electrolyte surface from a viscous-flow perspective. The
coupled relationships between current density and strain rate
directly impact stress accumulation at the solid−solid interface.
This has significant implications for the model of Porz et al.,26
where extrusion of Li metal out of structural heterogeneities on
the SE surface will contribute to the current-density depend-
ence of mechanical failure of the SE.
Furthermore, both nanoindentation37,38 and micropillar
compression39 experiments have reported that lithium can
support significantly higher stresses when confined to small
length scales. Using nanoindentation, Herbert et al. observed a
change in the underlying deformation mechanism as a function
of indentation depth.38 At shallow indentation depths, self-
diffusion dominated the flow, and at deeper depths, shear-
driven dislocation motion was the primary deformation
mechanism. Within the diffusive flow regime, the pressure
that Li is capable of supporting was found to be significantly
higher than the bulk yield stress and strongly dependent on the
strain rate, which is directly impacted by the current density.
Both of these results have implications for the propagation of
Li filaments within solid-state electrolytes. More research is
needed to understand the role that Li-metal mechanics plays
on filament formation and growth. In particular, improved
knowledge regarding Li purity (especially at the SE interface),
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Li mechanical properties, and how the morphology and
microstructure of Li metal change during electrochemical
cycling is needed.
Interphase Formation and Engineered Interfaces. Solid electro-
lyte redox stability depends on the alignment of the solid
electrolyte’s valence and conduction bands relative to the Li
chemical potential (μLi+) and decomposition thermodynam-
ics.40,41 Thus, most SEs will form an interphase at Li metal due
to redox reactions. The formation of interphase layers between
Li and SEs has widespread consequences for the operation of
SSBs. Many SEs under consideration are unstable in contact
with Li metal, and the evolution of the reacted interphase is
expected to be dependent on its transport properties.42−44 An
interphase that conducts both ions and electrons (a mixed
conductor) will continue to grow with time because of direct
electrochemical reaction occurring at the SE. An interphase
that conducts only ions and not electrons could grow to a
stable thickness, which would ideally result in a passivating
layer that enables long-term stability. An interphase with
insufficient ionic conductivity, however, will cause increased
impedance. Finally, for stability in contact with Li metal, the
interphase must prevent atomic Li diffusion from the Li anode
to the SE, which is challenging given the relatively high
diffusion rate of Li in many materials.
The chemo-mechanics of interphase formation and growth
have important ramifications for battery operation. Li insertion
and microstructural transformation during interphase growth
causes the evolution of mechanical stress both within the
interphase and within the SE.45,46 In SE materials where the
interphase grows to be relatively thick, such stresses can be
large enough to mechanically fracture the SE. Fracture of
Li1+xAlxGe2−x(PO4)3 (LAGP) caused by interphase growth was
recently monitored with in situ X-ray imaging, and it was found
that this mechanical degradation was the primary cause of
increased cell impedance, rather than the transport properties
of the interphase itself.47 The chemo-mechanics of interphase
The chemo-mechanics of interphase
formation is also important in the
context of electrochemical deposition
and stripping of Li metal, but this topic
has received less attention to date.
formation is also important in the context of electrochemical
deposition and stripping of Li metal, but this topic has received
less attention to date. For instance, stress within the interphase
or in the SE near the Li-metal interface could alter diffusion
barriers and pathways for Li ions. Furthermore, local variations
in interphase morphology could lead to stress nonuniformities
that may locally alter the potential, which could impact Li
deposition/stripping and lead to the formation of Li filaments
or dendrites.7 The interrelationship between interphase growth
and Li deposition/stripping mechanics thus requires dedicated
investigation by the community. To date, there have been two
primary approaches to mitigating interphase effects: (1)
engineering the lithium metal and/or (2) engineering an
interfacial layer material (e.g., interlayer).
One promising approach toward engineering the anode is
through controlled alloying. Li-rich alloys (e.g., Si, Sn, Al, Mg,
In, etc.) may play an important future role in SSBs. Such
materials have received significant attention as high-capacity
925
Perspective
anodes for liquid-based Li-ion batteries and are now being
integrated in small quantities into commercial graphite anodes
to boost capacity.48 In SSBs, they could be useful either as
interfacial layers or as anode active materials. In principle, alloy
materials can experience greater diffusion coefficients than
pure lithium. Recently, Li−Mg alloys were used to maintain
interfacial contact and increase Li utilization with no external
applied pressure in SSBs.49 Furthermore, Li−In alloys were
shown to be chemically stable against Li3PS4 when the alloy
remained in the two-phase region (In)-InLi.50 As described
previously, the mechanical properties of Li metal (e.g., creep
behavior) may not be sufficient to avoid delamination and pore
formation at high current densities.2,3 The addition of Li-alloy
interfacial layers in contact with Li-metal anodes could allow
for tuning of their mechanical and Li transport properties,
which could aid in maintaining uniform interfacial contact at
the SE interface. The use of high-capacity Li alloys as anodes
instead of Li metal is another potential route that could lead to
high-energy SSBs. Many Li alloys may be more stable in
contact with SEs because of their higher potentials compared
to the Li/Li+ redox couple.50 However, further research needs
to be carried out to understand the properties and structure of
interphases between SEs and Li alloys, especially as delithiation
kinetics and Li diffusivities at the interface will be different in
alloys compared to pure Li metal.
Engineered interfacial layers between Li metal and SEs can
aid in improving cell performance. Much of the work in this
area has focused on reducing interfacial impedance and
improving physical contact between Li and the SE. The two
primary routes to achieve these goals involve either introducing
a physical interlayer or controlling the surface chemistry of a
specific material (electrode or electrolyte).21,51 Interfacial
layers (interlayers), such as polymer coatings, can act as a
barrier film to decrease chemical decomposition at solid|solid
interfaces during electrochemical cycling and to promote
uniform Li deposition/stripping.52 Several coating strategies
are reported within the literature. A soft and flowable coating
can prevent the formation of cracks or pinholes in the SEI
layer.53 A highly elastic coating can regulate interface
uniformity by exerting high strength at high-strain areas.54
Additionally, a polymer coating with chemistries that can
mitigate the reactivity between the electrolyte and Li is
beneficial.55−57 These coatings are formed either ex situ or in
situ. Other strategies include adding a very soft polymer layer
underneath the current collector and Li instead of between Li
and the SE. The soft polymer layer can effectively diminish the
plating stress and prevent stress-driven dendrite growth.58
Besides interfacial layers, another strategy in which ceramic
ion conductors are combined with polymer ion conductors to
form hybrid membranes has been shown to enable more
compliant and tunable interfaces.59,60 In the hybrid approach,
the ceramic SE could provide a high mechanical modulus and
high ionic conductivity, and the polymer electrolyte could
provide ease of manufacture as well as improved adhesion and
stability with the electrodes.61 However, this approach requires
careful design and proper processing methods to be able to
take advantage of the advantageous properties of both the
polymer and the ceramic.61−64 In particular, the interface
between the polymer and the ceramic electrolytes needs to be
optimized.65,66
Alternatively, it may be feasible to design the SE to
decompose into a beneficial interphase without the need for an
additional interlayer. Ideally, such engineered interphases
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Figure 2. (a) Schematic of a measurement setup for pressure monitoring during solid-state battery operation.73 (b and c) Volume expansion
and contraction of the lithium metal anode during cycling results in large pressure changes and pressure oscillations.73 Reproduced with
permission from ref 73. Copyright 2018 The Royal Society of Chemistry. (d) Pressure-dependent impedance response of Li/LLZO/Li cells.
At high enough preforming pressure, the interface resistance between Li and LLZO can be mitigated. However, while preformation is
necessary, unless there is a constant applied pressure on the cell contact loss will occur during stripping experiments. Hence, high pressures
are needed for preformation; however, some external pressure is still needed to avoid pore formation.74 Panels d−f are reprinted from ref
74. Copyright 2019 American Chemical Society.

would prevent (electro)-chemical reaction between the SE and
Li while still allowing for Li-ion transport. This requires
materials that conduct ions, block electrons, and are (kineti-
cally) stable in contact with Li. While a variety of polymers,
ceramics, and even metals have been reported to improve the
stability of reactive SEs,35,67,68 characterizing the atomic
structure of the interphase that forms upon cycling is
challenging, and further efforts are necessary to elucidate the
interphase evolution in the presence of such protection layers.
Ultimately, strategies to mitigate deleterious interphase
formation need to be extended to roll-to-roll (R2R)
scales.69−71 Li metal forms a passivating surface film (even in
dry environments), and this film can lead to a high interfacial
resistance that can result in cell degradation. High interfacial
resistance must be minimized during manufacturing, if large Li-
metal foils are used in place of traditional anodes. Vapor
deposition or melt processing techniques can be used to create
a uniform layer of Li metal on top of the SE or interfacial
layers.72 However, depositing Li metal in this manner can drive
up manufacturing costs. These costs may be offset by the
inclusion of a smart manufacturing environment, where inline
quality control and environmental monitoring are used to
reduce manufacturing defects and increase overall cell yield. In
addition to manufacturing, the electrode architecture, cell
design, and packaging must be re-engineered for future SSBs
while considering the implications for both manufacturing and
high-performance cells.
Pressure during Operation and Formation in a Solid-State
Battery. SSBs rely on intimate contact between solid phases,
i.e., the active material and the SE, as well as possible additives
(Figure 2a). Charging and discharging leads to volume changes
in the anode and cathode active materials. In the case of the
anode, the volumetric expansion can be up to 300% for
extreme cases such as pure silicon, and even graphite
926
undergoes volume expansion of approximately 10% upon full
lithiation. The pressure oscillations due to volume change of a
Li-metal anode in a thioSSB are shown in Figure 2b,c, in which
solid−solid contacts will exhibit localized stresses. These local
tensile stresses lead to cracking and bending of SSBs if no
external pressure is used, ultimately resulting in contact loss
and poor battery performance. Thiophosphate-based SEs are
generally softer and more elastic (K/G > 1.75, where K is the
bulk modulus and G is the Shear modulus in GPa) than other
inorganic solid electrolytes (e.g., LLZO). The elasticity of the
SE will be important for decreasing fracture events in all-
inorganic cathodes73 and will likely affect the critical state
pressure.
Applying pressure to the SSB often occurs in two steps. First,
high pressure (which may also be accompanied by an elevated
temperature) can be applied during cell fabrication to initially
contact all components. Subsequently, a lower external
pressure is used during cycling to avoid contact loss.3 The
initial pressure required for formation depends on the
mechanical properties of the SE and active materials, as well
as the interfacial wetting properties with the Li anode. In
contrast, the external pressure during cycling only counteracts
the detrimental volume changes. Panels d−f of Figure 2 show
examples of these different scenarios. When using an Li/
LLZO/Li cell, the interface resistance between Li and LLZO
decreases and ultimately becomes negligible at 400 MPa of an
external preforming pressure.74 However, when using the Li/
LLZO/Li cell during stripping experiments, a reduced pressure
of 35 MPa is sufficient to retain good contact and prevent void
formation and morphological instabilities during stripping.74
For polymer electrolytes, a decrease in interfacial impedance
has also been observed with increasing stack pressure, until a
“critical stack pressure” is reached.72 Overall, the needed
pressure conditions during forming, the maintenance of stack
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Figure 3. Timeline of imaging and characterization of Li-metal|SE interfaces. Optical techniques (a) (Copyright 1999, Elsevier) and X-ray
tomography (b) reveal morphology of Li filaments at a polymer SE interfaces. (Reprinted by permission from ref 19. Copyright
2013Springer Nature.) Ex situ scanning electron microscopy revealed subsurface deposition in inorganic electrolytes (c and d). (Reproduced
with permission from ref 75. Copyright 2015 Elsevier.) Transmission electron microscopy experiments reveal structural transformation at
LLZO interfaces in contact with Li metal. (Reproduced from ref 76. Copyright 2016 American Chemical Society) Optical techniques
demonstrate dendritic growth of β-Li3PS4 polycrystals (Reproduced with permission from ref 26. Copyright 2017 Wiley) (f). Lithium metal
extruding out of intergranular regions (g) in LLZO (Copyright 2015, Elsevier) and microstructural representation of Li metal forming in
pores from X-ray tomography experiments (h). (Reproduced from ref 31. Copyright 2018 American Chemical Society.) Large mechanical
fracture of LAGP solid electrolyte (i) and evidence of lithium penetration across a LLZO electrolyte imaged with NMR (j). (Reproduced
from ref 77. Copyright 2019 American Chemical Society.) Neutron depth profiling enabling tracking of lithium at subsurface regions in a SE
(k). (Reproduced from ref 78. Copyright 2017 American Chemical Society.) Figure reproduced from refs 18, 19, 26, 31, 47, 75, and 77−80.

pressure under different operation conditions, and the
implications of these needed pressures on manufacturing
concerns are still open questions.
Diagnostics and Characterization Tools for Li|SE Interfaces.
Diagnostics tools and characterization techniques that can
probe subsurface phenomena are critical to improve our
understanding of the mechanistic origins of Li filament growth
and degradation pathways at solid|solid interfaces (Figure 3).
There are different opportunities for different characterization
techniques with respect to (1) technique spatial and temporal
resolution, (2) sample preparation and experiment character-
istic length scale, and (3) working environment. There are also
several mechanisms and processes that occur at different length
scales within a battery, and the resolution of the technique
(both temporal and spatial) provides boundaries for experi-
ments. Finally, the experimental working environment can
introduce transient and nonequilibrium conditions, especially if
the technique is destructive.
Over the last several years, there has been considerable
interest in characterizing physical and chemical transforma-
tions at solid|solid interfaces that contribute to interfacial
evolution and metal filament formation over a wide range of
time and length scales.26,75,79 While the theoretical basis for the
formation of passivating interphases is clear from the previous
discussion, the actual structure, chemistry, and transport
properties of interphases that form on the variety of SSE
materials are largely unknown.81 Recently, SE chemical
decomposition pathways when in contact with Li was
discerned using in situ X-ray photoelectron spectroscopy
(XPS) experiments82−84 and ex situ scanning electron and
optical microscopy has revealed filament formation within the
bulk SE (Figure 3a−d,f,g). In situ transmission microscopy
(TEM) (Figure 3e) has also revealed important information
about interfacial chemical and structural changes.52,76,81 In
cubic LLZO, for instance, a few-nanometer region near the
interface converts to the tetragonal phase because of Li
insertion.76 The NASICON-type LAGP material was found to
927
react and amorphize in contact with Li,81 with none of the
thermodynamically predicted compounds observed via dif-
fraction. Solid-state nuclear magnetic resonance (NMR)
spectroscopy has been employed to gain an understanding of
the composition85 of amorphous decomposition products
present at electrode|electrolyte interfaces and how these
species impact Li-ion transport in SSBs.86 Expanding the use
of other in situ/operando techniques well-suited to character-
izing amorphous phases will enable the investigation of
structural changes in a wider variety of SE materials. Because
of the highly heterogeneous and dynamic nature of interphase
formation it is desirable to couple theory and computation
with characterization to aid in experimental interpretation and
decrease experimental uncertainty. This is key to under-
standing interphase dynamics and will also inform the
engineering of artificial interphases with beneficial properties.
Beyond interphase characterization, there is a considerable
need to understand mesoscale material transformations
(delamination, filament growth, etc.). NMR techniques are
powerful tools for understanding Li microstructural growth
and Li-ion dynamics within SSBs.75 7Li NMR is able to
distinguish between 7Li resonances from the bulk Li electrode
and Li microstructures (filaments and/or dead Li).87
Furthermore, 7Li NMR combined with magnetic resonance
imaging (MRI) can enable 3D spatial tracking of Li filament
growth using 7Li chemical shift imaging (CSI). Marbella et al.
used ex situ 7Li CSI to correlate Li microstructural growth with
instabilities in galvanostatic cycling77 (Figure 3j). These
experiments showed heterogeneity at both interfaces, suggest-
ing the formation of local “hot spots” during Li stripping and
deposition. While the imaging dimension in these experiments
is limited to approximately 300 μm, NMR can provide
additional chemical resolution as well as enable in situ/
operando experimentation. Recently, in situ 3D 7Li MRI
experiments enabled tracking of local Li concentration
gradients within the bulk of Li10GeP2S12 (LGPS).88 These
experiments directly corroborated increases in interfacial
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resistances with Li concentration depletion at the anode
interface. NMR will continue to play a crucial role in SSB
characterization because of the unique ability of NMR to
identify disordered structural features89 that are often present
at interfaces, as well as to monitor Li-ion dynamics.90
X-ray computed tomography (XCT), like 3D 7Li MRI, is
also a 3D imaging technique but can achieve higher spatial
resolutions of <1 μm (micro-XCT) and <50 nm (nano-XCT).
Synchrotron XCT can be leveraged to carry out non-
destructive, in situ/operando measurements because of fast
acquisition times (Figure 3i,j).15,17,19,31 The key drawback of
this technique is the lack of chemical specificity toward Li.
Thus, only indirect observation of filament growth can be
achieved. Neutron depth profiling (NDP) (Figure 3k) is
another tool to investigate Li-metal deposits near the anode|
electrolyte interface. NDP is a near-surface analysis technique
that employs cold neutrons to excite Li to emit α particles and
protons which are subsequently detected.3 NDP is a
nondestructive tool that can offer insight into Li concen-
trations near the interfacial region with micrometer-level
resolution. However, NDP is currently limited in its ability
to track deposition within the bulk and in its ability to track
local structural characteristics.
Most of the characterization techniques used to investigate
chemical, physical/mechanical, and microstructural trans-
formations at Li|SE interfaces have focused on a singular
aspect of the system. Experimental results have conclusively
Experimental results have conclusively
shown a strong codependence be-
tween material transformations and
electrochemical performance. Thus, it is
vital to pursue multimodal character-
ization in order to achieve comple-
mentary datasets on coupled phe-
nomena. Coupling techniques like
atomic force microscopy with spec-
troscopy can provide simultaneous
information regarding mechanical,
structural, and chemical properties.
shown a strong codependence between material trans-
formations and electrochemical performance. Thus, it is vital
to pursue multimodal characterization in order to achieve
complementary datasets on coupled phenomena. Coupling
techniques like atomic force microscopy with spectroscopy can
provide simultaneous information regarding mechanical,
structural, and chemical properties. Synchrotron techniques
also offer high versatility in terms of combining techniques to
probe multiple phenomena at varying length scales; for
example, transmission X-ray microscopy coupled with X-ray
absorption near edge structure (XANES), or microtomography
coupled with X-ray diffraction/absorption spectroscopy.
Operando optical video microscopy can be synchronized with
voltage signatures during cycling to provide insights into
electrochemical signatures of Li filament propagation.72 In the
future, operando and in situ measurements coupled with theory
and computation will continue to offer new insights into the
dynamic, coupled phenomena occurring in these systems.
928
Perspective
Modeling. Advanced modeling of SSBs is critical for the
interpretation of experiments, probing transport mechanisms,
and describing the phenomenological origin of interfacial
transformations. Mechanical stresses at the Li|SE interface are
intrinsic to SSBs, which point toward adopting rigid barriers as
a possible strategy for dendrite mitigation. The complexities of
ion transport in the electrolyte, reaction kinetics, and
mechanics due to stress generation at the Li|SE interface
need to be understood to correlate with changes in SSB
performance (Figure 4a).
Transport behavior in all-inorganic and all-polymer electro-
lytes has been explored at the continuum scale, yet
formulations for stress-induced modifications to ion transport
have yet to be identified. The effects of stress on transport in
the SE are likely important, which may be analogous to stress
effects on Li diffusion during intercalation events.91 Accurate
experimental determination of ionic conductivity as a function
of external pressure as well as transport properties are
necessary for building effective models for all inorganic or
polymer SSBs. Furthermore, operando and in situ experimenta-
tion which combines real space imaging techniques with
electrochemistry and transport measurements will aid in the
development of accurate mesoscale models (Figure 4b−d).
While transport mechanisms at the continuum level are well
understood for homogeneous SEs, less is known about
transport in hybrid composite SEs. The ion transport behavior
in inorganic/polymer composites is complex and provides a
rich design space to explore and optimize.63,64,92 Developing a
molecular-scale understanding of ion transport at the interface
of polymer−ceramic composites could help to develop high-
performing composite electrolytes that can manifest the
benefits of inorganic and polymeric materials.92 Recently,
effective mean field theory (EMFT) approaches combined
with experimentally obtained ionic conductivity measurements
were used to map ion transport pathways in hybrid SEs.63
While EMFT provides a pathway for discerning between
anionic and cationic transport pathways at complex inorganic/
organic interfaces, it does not include solvation/desolvation
mechanisms and polymer physics. Advanced modeling and
experiments are necessary to deconvolve transport mechanisms
between polymer and ceramic ion conductors.
Monroe and Newman proposed the first model of stress-
kinetics coupling by correlating the exchange current density
from Butler−Volmer kinetics at the Li−polymer interface with
the electrochemical potential change through interfacial
hydrostatic/deviatoric stresses and molar volume mismatch.6,7
Furthermore, linear elastic perturbation analysis on a static
metal−polymer system incorporating the stress-kinetic for-
mulations was used to determine a threshold shear modulus of
SEs for stable deposition, precluding transport effects. Barai
and Srinivasan extended this model to incorporate transport,
plastic Li deformation, and external pressure effects.8,93 Model
reformulation for inorganic SEs to delineate stability regimes,
as well as accounting for the polycrystalline microstructure of
the SE, has been explored as well.11,94−96 First-principles
studies have also proposed a mechanism for Li-metal
penetration through polycrystalline solid electrolytes based
on grain boundary softening.97 However, studies have yet to
ascertain a singular root cause of the CCD observed across all
classes of inorganic electrolytes, whether single-crystal or
polycrystalline. Recently, Griffith’s theory based on linear
elastic fracture mechanics has been proposed to understand the
mechanism of lithium metal penetration through inorganic
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ACS Energy Lett. 2020, 5, 922−934
ACS Energy Letters http://pubs.acs.org/journal/aelccp Perspective

Figure 4. Advanced mesoscale models that combine experimentally obtained properties (transport, kinetics, interfacial properties, and
mechanics) are necessary for discerning fundamental transformations in all-solid-state batteries (a). Operando experiments that combine real
space imaging techniques (b−d) can provide a basis for modeling domains (Reproduced from ref 98. copyright 2019 American Chemical
Society). Nonequilibrium meso-structural transformation is important for building effective models. Schematic of polycrystalline SE
sandwiched between Li-metal electrodes in symmetric cell configuration with (e) corresponding microstructure phase map consisting of
grains, voids, and grain boundaries (GB) and (f) damage map exhibiting fracture concentration along the grain boundaries with
electrodeposition under the constrained configuration.

solid electrolytes, correlating the lithium plating overpotential
to the surface defect size and fracture toughness of the
electrolyte.26 This theory gives contrasting results to the
Monroe−Newman model; high Young’s modulus solid
electrolyte metal is associated with lower CCDs through
higher magnitudes stress-based crack opening. It is the authors’
opinion that a reconcilement of the two theories can be
achieved through incorporation of pertinent interfacial physics
to the models, including chemical/mechanical wettability and
contact/fracture mechanics resulting from inherent interfacial
surface roughness.
It is imperative to note that there is an ongoing debate in the
scientific community with regards to the molar volume inside
the inorganic solid electrolyte. Zero molar volume has been
reported for LLZO in the literature based on negligible
volumetric change with Li+ incorporation, alongside a wide
range of values for different SEs.94,95 Ahmad et al. has
delineated the stability regime of inorganic solid electrolytes as
a function of solid electrolyte to Li-metal molar volume and
shear modulus ratio and has shown that inorganic solid
electrolytes with low molar volume and high shear moduli
ratios (such as LPS or LLZO) are prone to current
instabilities.11 A bridge needs to be built between the
molecular scale definitions of molar volume with those used
in continuum models; in particular, there is a lack of consensus
as to whether to correlate molar volume to the cationic/
anionic radii or to consider it as an inherent part of the crystal
structure.
Detailed insights into the performance of SSBs through
modeling requires a dynamic model that is capable of temporal
tracking of deposition/stripping at the interface which includes
the interactions emanating from elastic−plastic stresses, ion
transport, and electrochemistry. Furthermore, incorporation of
chemical (surface tension) and mechanical wettability
(external pressure), imperfect contact/peeling, and micro-
structural heterogeneities (e.g., voids, grains, grain boundaries
for a polycrystalline electrolyte) into the modeling paradigm
will help elucidate the scenarios that limit performance (Figure
4e,f). The presence of an interphase/interlayer between the
metal and SE will add to the model complexity, requiring
stresses and transport to be solved in an additional layer, while
929
accounting for characteristics of the layer (brittle/ductile
deformation, Maxwell/Ohm transport law, Butler−Volmer/
Tafel kinetics, etc.). First-principles studies catalyzed by
machine learning approaches will also be useful in rapid
estimation of the transport, mechanical, and thermodynamic
properties of the SE materials.99 First-principles atomistic
calculations utilizing density functional theory catalyzed by
machine learning approaches will also be useful in rapid
estimation of the transport (ionic conductivity/diffusivity),
mechanical (stiffness tensor), kinetic (exchange current
density), and thermodynamic (molar volume) properties of
the SE materials.99 In the literature, density functional theory
has proven useful in estimating the ionic conductivity and
Young’s modulus of both amorphous and polycrystalline solid
electrolyte materials100,101 Our conjecture and proposition is
that dynamic mesoscale interactions,102−105 including the
interplay between reaction kinetics, interfacial stochasticity,
transport, and mechanics, are essential to provide fundamental
mechanistic insights into Li-metal-based SSBs (Figure 4e).
Outlook and Future Directions. To date, the majority of work
on Li filament formation in SSBs has focused on characterizing
Li plating/stripping in Li/Li symmetrical cells. Interfacial
phenomena that are key to filament nucleation and growth
may differ substantially in full cells, emphasizing the need to
expand these characterization techniques to more realistic
systems. Furthermore, the formation of heterogeneous
interphases can lead to stress nonuniformities that impact
the local accumulation of stripping and/or deposition
products. While there are many potential pathways toward
mitigating lithium filaments (e.g., Li alloys, pressure, and SE
strength), maintaining uniform contact between the electrode
and SE is paramount. Characterization and control over the
atomic structure of the interphase will be important for
addressing chemo-mechanical challenges at solid|solid inter-
faces. Advanced techniques that combine real and reciprocal
space experimental techniques with modeling may provide a
means for probing the variety of length scales that exist in a
solid-state battery at realistic temporal and spatial length scales.
There is also an emerging need for standardization of
experimental methods across the community. Communication
of protocols and operating conditions (Li-metal thickness,
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ACS Energy Lett. 2020, 5, 922−934
ACS Energy Letters http://pubs.acs.org/journal/aelccp
temperature, pressures, etc.) will be paramount for inter-
pretation of results within this rapidly growing community,
with the ultimate goal of achieving lithium−solid electrolyte
interfaces for solid-state battery operation.
■ AUTHOR INFORMATION
Corresponding Author
Kelsey B. Hatzell − Department of Mechanical Engineering,
Interdiscplinary Department of Material Science, and
Department of Chemical and Biomolecular Engineering
Engineering, Vanderbilt University, Nashville, Tennessee 37202,
United States; orcid.org/0000-0002-5222-7288;
Email: Kelsey.b.hatzell@vanderbilt.edu
Authors
Xi Chelsea Chen − Chemical Sciences Division, Oak Ridge
National Laboratory, Oak Ridge, Tennessee 37830, United
States; orcid.org/0000-0003-1188-7658
Corie L. Cobb − Department of Mechanical Engineering,
University of Washington, Seattle, Washington 98195, United
States
Neil P. Dasgupta − Department of Mechanical Engineering,
University of Michigan, Ann Arbor, Michigan 48103, United
States; orcid.org/0000-0002-5180-4063
Marm B. Dixit − Department of Mechanical Engineering and
Interdiscplinary Department of Material Science, Vanderbilt
University, Nashville, Tennessee 37202, United States
Lauren E. Marbella − Department of Chemical Engineering,
Columbia University, New York, New York 10027, United
States; orcid.org/0000-0003-1639-3913
Matthew T. McDowell − G. W. Woodruff School of Mechanical
Engineering, Atlanta, Georgia 30332, United States; School of
Materials Science and Engineering, Atlanta, Georgia 30332,
United States; orcid.org/0000-0001-5552-3456
Partha P. Mukherjee − School of Mechanical Engineering,
Purdue University, West Lafayette, Indiana 47907, United
States
Ankit Verma − School of Mechanical Engineering, Purdue
University, West Lafayette, Indiana 47907, United States
Venkatasubramanian Viswanathan − Department of
Mechanical Engineering, Carnegie Mellon University, Pittsburgh,
Pennsylvania 15213, United States; orcid.org/0000-0003-
1060-5495
Andrew S. Westover − Chemical Sciences Division, Oak Ridge
National Laboratory, Oak Ridge, Tennessee 37830, United
States
Wolfgang G. Zeier − Institute of Physical Chemistry and Center
for Materials Research (LaMa), Justus-Liebig-University
Giessen, D-35392 Giessen, Germany; orcid.org/0000-0001-
7749-5089
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsenergylett.9b02668
Notes
The authors declare no competing financial interest.
Biographies
Kelsey B. Hatzell is an assistant professor at Vanderbilt University
with appointments in Mechanical and Chemical and Biomolecular
departments. Hatzell has received numerous awards, including the
NSF CAREER award, ECS Toyota Young Investigator Award, and
MRS Nelson “Buck” Robinson Award. Her research interests focus on
understanding transport in solid-state batteries.
930
Perspective
X. Chelsea Chen is a staff scientist in the Energy Storage and
Membrane Materials Group at Oak Ridge National Lab. Her fields of
expertise are polymer physics, ion transport in polymers, and
structural and morphological characterizations. Her current research
focuses on developing polymer−ceramic composite electrolytes and
understanding polymer/ceramic interfaces.
Corie L. Cobb is the Washington Research Foundation Innovation
Professor in Clean Energy and Associate Professor of Mechanical
Engineering at the University of Washington. She is a recent recipient
of a 2019 DARPA Young Faculty Award and a 2019 3M Non-
Tenured Faculty Award. Her current research focuses on computa-
tional design and manufacturing solutions for 3D and solid-state
Lithium-ion batteries.
Neil Dasgupta is an Assistant Professor in the Department of
Mechanical Engineering at the University of Michigan. He has
received numerous awards, including the NSF CAREER award,
DARPA Young Faculty Award, and AFOSR Young Investigator
Award (YIP). His research focuses on the intersection of materials
chemistry, electrochemical energy storage, and nanomanufacturing.
Marm B. Dixit is a doctoral candidate of Mechanical Engineering at
Vanderbilt University. He is working on multimodal solid-state
batteries using synchrotron techniques. He has published nearly 20
journal articles on electrochemical systems.
Lauren E. Marbella is an Assistant Professor of Chemical Engineering
at Columbia University. Her group uses NMR and MRI to
understand interfacial phenomena and structure-performance rela-
tionships in systems for electrochemical energy storage and
conversion.
Matthew T. McDowell is an assistant professor at Georgia Tech with
appointments in the G. W. Woodruff School of Mechanical
Engineering and the School of Materials Science and Engineering.
McDowell has over 70 publications and has received numerous
awards, including the Presidential Early Career Award for Scientists
and Engineers (PECASE), the Sloan Fellowship, the NSF CAREER
Award, and the NASA Early Career Faculty Award.
Partha P. Mukherjee is currently an Associate Professor of
Mechanical Engineering at Purdue University. Prior to that, he held
positions at Texas A&M University and Oak Ridge and Los Alamos
National Laboratories. His research is focused on mesoscale physics
and stochastics of transport, chemistry, and microstructure
interactions in energy storage and conversion.
Ankit Verma is a doctoral candidate of Mechanical Engineering at
Purdue University. He is working on multimodal degradation
mechanisms and interactions in lithium intercalation and metal
batteries. He has authored/coauthored more than 10 journal papers
on batteries and energy storage.
Venkat Viswanathan is an Associate Professor of Mechanical
Engineering at Carnegie Mellon University. He is a recipient of
numerous awards including the Alfred P. Sloan Fellowship, Office of
Naval Research Young Investigator Award, and National Science
Foundation CAREER award. He leads an interdisciplinary group
working on advanced batteries for electric vehicles, trucks, and plane
Andrew Westover is a Staff Scientist in the Chemical Sciences
Division at Oak Ridge National Laboratory. His research focuses on
the development of solid-state batteries with an emphasis on Li-metal
anodes, interfaces, and solid-state electrolytes.
Wolfgang G. Zeier is a junior group leader at the Justus-Liebig
University Giessen, within the framework of an Emmy-Noether
research group. His research interests encompass the fundamental
https://dx.doi.org/10.1021/acsenergylett.9b02668
ACS Energy Lett. 2020, 5, 922−934
ACS Energy Letters http://pubs.acs.org/journal/aelccp
structure−property relationships in solids, with a focus on thermo-
electric and ion-conducting materials, as well as solid−solid interfacial
chemistry in all-solid-state batteries.
■
ACKNOWLEDGMENTS
K.B.H and M.B.D. acknowledge support from National Science
Foundation grant No. 1847029. P.P.M and A.V. acknowledge
support from Grant No. 1805656. K.B.H, N.P.D., L.E.M,
M.T.M, P.P.M, and V.V. acknowledge support from the
Research Corporation for Scientific Advancement (Scialog
program in Energy Storage). X.C.C. acknowledges support
from U.S. Department of Energy (DOE), Office of Energy
Efficiency and Renewable Energy for the Vehicle Technologies
Office’s Advanced Battery Materials Research Program as well
as Office of Sciences, Basic Energy Sciences, Materials Science
and Engineering Division. V.V. acknowledges support from the
Advanced Research Projects Agency Energy (ARPA-E) under
Grant DE-AR0000774. A.S.W. acknowledges support from the
ARPA-E IONICS program Award No. DE-AR0000775. N.P.D.
acknowledges support from an ECS Toyota Young Investigator
Fellowship.
■
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